CN111484141B - Degradation method of bromocresol green wastewater - Google Patents
Degradation method of bromocresol green wastewater Download PDFInfo
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- FRPHFZCDPYBUAU-UHFFFAOYSA-N Bromocresolgreen Chemical compound CC1=C(Br)C(O)=C(Br)C=C1C1(C=2C(=C(Br)C(O)=C(Br)C=2)C)C2=CC=CC=C2S(=O)(=O)O1 FRPHFZCDPYBUAU-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000002351 wastewater Substances 0.000 title claims abstract description 30
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 29
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000001963 growth medium Substances 0.000 claims abstract description 21
- 230000000593 degrading effect Effects 0.000 claims abstract description 10
- 230000005611 electricity Effects 0.000 claims abstract description 4
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- 239000002105 nanoparticle Substances 0.000 claims description 5
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- 229920001817 Agar Polymers 0.000 description 2
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/005—Combined electrochemical biological processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a method for degrading bromocresol green wastewater, which belongs to the technical field of sewage treatment and is characterized in that light is used for exciting nano-material titanium dioxide and electrogenesis microorganismsS.oneidensisMR-1 is used to construct a new biological photoelectric reduction system, which mainly comprises the following steps of generating electricity by microorganismsS.oneidensisThe MR-1 is connected into a decoloration culture medium containing nano titanium dioxide for anaerobic reaction, and in the reaction process, electrogenesis microorganismsS.oneidensisElectrons generated by MR-1 anaerobic respiration are transferred to photo-excited nano material titanium dioxide through self non-specific release, the titanium dioxide is excited under the light radiation of UVA to generate electrons, and the electrons are finally transferred to bromocresol green, so that the bromocresol green is degraded; the novel degradation system constructed by the invention successfully solves the problem of insufficient photo-generated electrons of the nano titanium dioxide under anaerobic conditions, and realizes the efficient degradation of the bromocresol green wastewater.
Description
Technical Field
The invention relates to a method for degrading bromocresol green wastewater, in particular to a method for degrading bromocresol green wastewater by exciting nano material titanium dioxide and electrochemical active microorganisms through lightShewanellaoneidensisMR-1 constructs a novel biological photoelectric reduction system to realize efficient degradation of bromomethylA method for phenol green wastewater, belonging to the technical field of sewage treatment.
Background
The bromocresol green wastewater mainly comes from industries such as dye, biochemistry and medicine, and the wastewater generated in the fields is complex in components and various in types. In reality, the places usually carry out mixed treatment on the wastewater, the wastewater treatment often lacks a targeted effective means, and the treated wastewater hardly meets the increasingly strict national discharge requirements. And the bromocresol green wastewater is a pollutant which is difficult to degrade and harmful, and can damage the environment if the bromocresol green wastewater cannot be effectively treated and discharged into the environment.
The main method adopted for researching the bromocresol green wastewater treatment at present is the photocatalytic degradation of nano materials, and the nano titanium dioxide is the most common photocatalyst applied in the current environmental pollution treatment due to the advantages of low cost, low toxicity, good photocatalytic performance, high stability and the like. But the photo-oxidative degradation of the dye by utilizing a cavity formed by illumination under the aerobic condition is not beneficial to the reduction and decoloration of the dye; when the photocatalytic degradation is carried out under the completely anaerobic condition, the holes can not be neutralized in time, the generation of photo-generated electrons can be influenced, and finally, the photoreduction degradation effect on complex organic matters is poor.
Disclosure of Invention
The invention aims to provide a method for improving the degradation efficiency of light-excited nano-material titanium dioxide on bromocresol green wastewater.
The invention relates to a method for preparing nano titanium dioxide and electrochemically active microorganismsS.oneidensisMR-1 is combined to construct a novel biological photoelectric reduction system, thereby establishing a novel method for efficiently degrading bromocresol green wastewater. In the present invention, electrochemically active microorganismsS.oneidensisElectrons generated by MR-1 anaerobic respiration are transferred to the titanium dioxide of the photo-excitation nano material through self non-specific release, the titanium dioxide is excited under the light radiation of UVA to generate electrons, and the electrons are finally transferred to bromocresol green, so that the degradation capability of the titanium dioxide to the bromocresol green is improved, and the degradation process is shown in figure 1.
The light-excited nano material is dioxideTitanium nanoparticles, the electrochemically active microorganisms beingS.oneidensisMR-1, the contaminant is bromocresol green.
The invention provides a degradation method of bromocresol green wastewater, in particular to a method for degrading light-excited nano-material titanium dioxide and electrogenesis microorganismsS.oneidensisThe method for improving the degradation of bromocresol green wastewater by combining MR-1 comprises the following steps:
(1) electricity-producing microorganismS.oneidensisCollecting the thalli after the MR-1 is subjected to shake culture, resuspending thalli sediment by using a mineral salt culture medium, and adjusting the concentration of the thalli to 4-6 multiplied by 107 CFU/mL；
Wherein the electrogenic microorganismsS.oneidensisThe MR-1 cells were prepared as follows:
preparing solid plate LB culture medium (containing yeast extract 5g/L, tryptone 10g/L, sodium chloride 10g/L, agar 2%),S.oneidensisMR-1 was incubated overnight at 30 ℃;
will be activatedS.oneidensisThe MR-1 strain is inoculated in 50mL liquid LB culture medium (the culture medium does not contain agar), shake culture is carried out in a shaker at 30 ℃ and 200 rpm until logarithmic phase, and then the cultured bacterium liquid is centrifuged at 7000 rpm for 15min to collect thalli.
The formula of the mineral salt culture medium is as follows: the culture medium contains 7.5 mmol NaOH and 28 mmol NH per liter4Cl、1.3 mmolKCl、4.3 mmol NaH2PO4100 mmol NaCl, 1 mL of vitamin mother liquor, 1 mL of amino acid mother liquor and 1 mL of trace element mother liquor; reference is made to the Bretscher O, Obraztsova A, Sturm C A, et al. Current production and metal oxide production byShewanellaoneidensisMR-1 wild type and mutants[J]. Applied and Environmental Microbiology, 2007, 73(21): 7003-7012）。
(2) Inoculating the bacterial liquid obtained in the step (1) into a mineral salt culture medium containing nano titanium dioxide and bromocresol green, introducing high-purity nitrogen for 15min to remove oxygen, and then sealing;
the culture medium contains titanium dioxide nanoparticles and bromocresol green 50 mg/L;
the electricity-generating microorganismS.oneidensisThe dosage of the MR-1 bacterial liquid is 1.2 mL;
the preparation of the mineral salt culture medium containing nano titanium dioxide and bromocresol green is as follows:
0.001 g of bromocresol green was weighed and dissolved in 20mL of mineral salt medium to give a final concentration of 50mg/L of bromocresol green.
0.001 g of nano titanium dioxide is weighed and suspended in a prepared mineral salt culture medium containing bromocresol green, and the mixed solution is subjected to ultrasonic treatment for 30min by using an ultrasonic cleaner, so that titanium dioxide nano particles are uniformly dispersed in the solution to reach the final concentration of 50 mg/L.
(3) And (3) placing the sealed mixed solution obtained in the step (2) in a dark dry environment, placing the mixed solution into a shaking table after the mixed solution achieves adsorption balance on bromocresol green, reacting at the temperature of (30 +/-0.5) and the rpm of (200 +/-5), and carrying out UVA illumination treatment on the mixed solution.
The invention has the following beneficial effects:
the selected electrochemical active microorganism is a microorganism which can utilize various organic matters as a carbon source, release electrons generated by metabolism to the surrounding environment through the self anaerobic respiration action, directly contact with an extracellular electron acceptor, or transfer the electrons to the electron acceptor through the action of an electron transmitter to perform dissimilatory anaerobic respiration. Modularly electrogenic microorganismsS.oneidensisMR-1 is a facultative anaerobic gram-negative bacterium that not only can utilize oxygen as an electron acceptor for aerobic respiration, but also can utilize various substances in the environment, such as dyes, etc., as electron acceptors for anaerobic respiratory metabolism under anaerobic conditions. Therefore, the invention excites the titanium dioxide of the nano material and the electricity generating microorganism with lightS.oneidensisMR-1 is combined to construct a novel biological photoelectric reduction system. Under anaerobic conditionsS. oneidensisThe MR-1 releases electrons through the self anaerobic respiration action and transfers the electrons to the nano titanium dioxide, thereby playing the aim of supplementing the electrons to the nano titanium dioxide, and finally the nano titanium dioxide transfers the electrons to the bromocresol green wastewater, thereby improving the degradation capability of the nano titanium dioxide to the bromocresol green wastewater.
The invention can degrade bromocresol by combining nano titanium dioxideGreen waste water and electrogenesis microorganismS.oneidensisMR-1 can carry out nonspecific electron release, and a novel nano titanium dioxide and electrogenic microorganism are constructedS.oneidensisMR-1 reduction system. The problem that photo-generated electrons of the nano titanium dioxide are insufficient under anaerobic conditions is solved, and the degradation efficiency of the nano titanium dioxide on the bromocresol green wastewater is greatly improved. And an effective means for the treatment of the bromocresol green wastewater is provided, so that the efficient degradation of the bromocresol green wastewater is realized.
Drawings
FIG. 1 is a constructed nano titanium dioxide andS.oneidensisa mechanism diagram of the MR-1 novel reduction system for degrading bromocresol green.
FIG. 2 is a constructed nano-titania andS.oneidensisa full spectrogram of degradation of bromocresol green by an MR-1 novel reduction system and a control group.
FIG. 3 is a constructed nano-titania andS.oneidensisthe degradation efficiency of the MR-1 novel reduction system and a control group to bromocresol green is shown.
FIG. 4 shows the constructed nano-titanium dioxide andS.oneidensisthe degradation rate of the MR-1 novel reduction system and a control group to bromocresol green is shown.
In the figure, dye represents bromocresol green; the degradation time is 12 h.
Detailed Description
The technical solutions of the present invention are further explained below with reference to specific examples to enable those skilled in the art to better understand the technical solutions, but the scope of the present invention is not limited thereto.
The strain of the inventionS.oneidensisMR-1 is a model electrochemically active microorganism, donated by professor Nielsen, university of California, USA, deposited at the American model type Collection center (ATCC), strain number ATCC700500TMThe strain can be purchased directly from the center. The used light-excited nano material is commercially available titanium dioxide nano particles; the contaminant used was analytically pure bromocresol green.
The solid plate LB culture medium, the mineral salt culture medium and the solid plate PDA culture medium are all commonly used in the field and can be purchased or prepared according to the conventional formula.
Example (b):
efficient degradation method of bromocresol green wastewater and electrogenic microorganismsS.oneidensisElectrons generated by MR-1 anaerobic respiration are transferred to the photo-excited nano-material titanium dioxide through self non-specific release. The nanometer titanium dioxide is excited under the light radiation of UVA to generate electrons, and the electrons are finally transferred to the bromocresol green, so that the efficient degradation of the bromocresol green is realized.
The specific implementation steps are as follows:
(1) to be stored in glycerin pipeS.oneidensisMR-1 was streaked onto solid LB plates and incubated overnight at 30 ℃.
(2) Activated by suction with pipetteS.oneidensisThe MR-1 single colony is inoculated in 50mL liquid LB culture medium, shake culture is carried out in a shaker at 30 ℃ and 200 rpm until logarithmic phase, and then the cultured bacterium liquid is centrifuged at 7000 rpm for 15min to collect the bacterium. Resuspending the thallus precipitate with mineral salt culture medium, and adjusting the thallus concentration to 4-6 × 10 with visible spectrophotometer7CFU/mL, spare.
The formula of the mineral salt culture medium is as follows: the culture medium contains 7.5 mmol NaOH and 28 mmol NH per liter4Cl、1.3 mmolKCl、4.3 mmol NaH2PO4100 mmol NaCl, 1 mL of vitamin mother liquor, 1 mL of amino acid mother liquor and 1 mL of trace element mother liquor; reference is made to the Bretscher O, Obraztsova A, Sturm C A, et al. Current production and metal oxide production byShewanellaoneidensisMR-1 wild type and mutants[J]. Applied and Environmental Microbiology, 2007, 73(21): 7003-7012）。
(3) 0.01 g of bromocresol green is weighed and dissolved in 200mL of mineral salt culture medium to obtain a mixed solution, and an experimental group is set up (titanium dioxide and titanium dioxide are added simultaneouslyS.oneidensisMR-1 with UVA illumination), negative control group A (titanium dioxide only, UVA illumination), and negative control group B (only UVA illumination)S.oneidensisMR-1), negative control group C (UVA only illumination) and negative control group D (titanium dioxide only, no UVA illumination) five per groupParallel.
And (3) respectively adding 1.2mL of the bacterial liquid prepared in the step (2) into the experimental group and the negative control group B, introducing high-purity nitrogen into the solution for 15min for the experimental group and all the control groups, and then sealing.
(4) And (4) putting the mixed solution prepared in the step (3) into a shaker at 30 ℃ and 200 rpm for culturing, and switching the experimental group, the negative control group A and the negative control group C into UVA light for treatment.
(5) The experimental group and the control group are sampled (strictly requiring anaerobic property), and the light absorption value and the full spectrogram of the sampled products are measured by using a visible spectrophotometer and an ultraviolet spectrophotometer.
(6) The degradation rate (expressed as decolorization rate) and the average degradation rate (mg/h) were calculated according to formula (1) and formula (2), respectively.
Decolorization ratio (%)
（1）
In the formula (I), the compound is shown in the specification,A 0、A trespectively the absorbance of the initial and degradation t times of the dye solution; (ii) aC 0、C tRespectively the concentrations of the dye in the system after the initial time and the degradation time t, mg/L;Vis the volume of the system, L; t is the degradation time, h. Each experiment was repeated five times. The full spectrogram, degradation rate chart and degradation rate chart of degradation of bromocresol green of the experimental group and the negative control group are respectively shown in figures 2, 3 and 4, and the degradation time is 12 h.
As can be seen from FIG. 2, bromocresol green is used for constructing nano titanium dioxide andS.oneidensisthe maximum absorption peak of the MR-1 novel reduction system completely disappears, and the maximum absorption peak of bromocresol green under the action of the negative control group A, B, C, D still exists. This indicates the nano-titanium dioxide andS.oneidensisthe MR-1 novel reduction system can completely degrade bromocresol greenWhile the other negative controls were only able to partially degrade bromocresol green.
As can be seen from FIG. 3, the nano-titanium dioxide and the titanium oxide are constructedS.oneidensisThe degradation rate of the MR-1 novel reduction system to bromocresol green is 99.29%, while the degradation rate of a control group A (only titanium dioxide is added and UVA illumination is carried out) is only 53.14%, and the degradation rate of a control group B (only titanium dioxide is added and UVA illumination is carried out)S.oneidensisMR-1), control C (UVA light only) and control D (titanium dioxide added without UVA light only) were only 7.86%, 3.46% and 12.03%, respectively.
As can be seen from FIG. 4, the constructed nano-titania and nano-titaniaS.oneidensisThe degradation rate of the MR-1 novel reduction system to bromocresol green is 4.137mg/h, is obviously larger than that of all control groups, is 1.87 times of that of control group A (only titanium dioxide is added and UVA illumination is carried out), and control group B (only titanium dioxide is added and UVA illumination is carried out)S.oneidensisMR-1), 29.34 times control C (UVA light only), and 8.27 times control D (titanium dioxide added only without UVA light).
As can be seen from the above, the results of FIGS. 2-4 show that the titanium dioxide and the titanium dioxide are mixedS.oneidensisThe novel biological photoelectric reduction system constructed by MR-1 successfully solves the problem of insufficient photo-generated electrons of nano titanium dioxide under anaerobic conditions, remarkably improves the degradation efficiency and the degradation rate of titanium dioxide on bromocresol green wastewater, and realizes the efficient degradation of the bromocresol green wastewater, thereby establishing a novel method for efficiently degrading the bromocresol green wastewater. Therefore, the method for degrading bromocresol green wastewater provided by the patent is completely feasible.
Claims (6)
1. A method for degrading bromocresol green wastewater is characterized in that nano titanium dioxide and electrogenesis microorganisms are mixedS.oneidensisMR-1 is used for degrading bromocresol green wastewater;
the method comprises the following steps:
(1) electricity-producing microorganismS.oneidensisCollecting thalli after the MR-1 is subjected to shake culture, carrying out heavy suspension on thalli precipitates by using a mineral salt culture medium, and adjusting the concentration of the thalli;
(2) inoculating the bacterial liquid obtained in the step (1) into a mineral salt culture medium containing nano titanium dioxide and bromocresol green, introducing high-purity nitrogen to remove oxygen, and then sealing;
(3) and (3) placing the sealed mixed solution obtained in the step (2) in a dark dry environment, placing the mixed solution in a shaking table after the mixed solution achieves adsorption balance on bromocresol green, and carrying out UVA illumination treatment on the mixed solution.
2. The method of claim 1, wherein the electrogenic microorganismsS.oneidensisThe bacterial density of the MR-1 is 4-6 x 107 CFU/mL。
3. The method according to claim 1, wherein the amount of the electrogenic microorganism MR-1 inoculated into the mineral salt medium containing nano titanium dioxide and bromocresol green is 200mL, and 1.2mL of the electrogenic microorganism MR-1 is inoculated into the medium.
4. The method as claimed in claim 1, wherein the mineral salt medium containing nano titanium dioxide and bromocresol green contains titanium dioxide nanoparticles with a final concentration of 50mg/L and bromocresol green with a final concentration of 50 mg/L.
5. The method according to claim 1, wherein the mixed solution is purged with high-purity nitrogen gas for 15 min.
6. The method of claim 1, wherein the mixed solution is subjected to UVA light treatment in a shaker at 30 + 0.5 ℃ and 200 + 5 rpm.
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